U.S. patent number 4,361,435 [Application Number 05/935,594] was granted by the patent office on 1982-11-30 for copper and amine based aquatic herbicides.
This patent grant is currently assigned to Sandoz, Inc.. Invention is credited to Marion D. Meyers, Graham A. Stoner.
United States Patent |
4,361,435 |
Meyers , et al. |
November 30, 1982 |
Copper and amine based aquatic herbicides
Abstract
Herbicidal and algaestatic and algaecidal compositions and use
thereof comprising copper salts; both soluble acid salts as copper
sulfate, chloride, nitrate, acetate, sulfamate, gluconate, citrate,
etc. and basic copper salts such as basic copper sulfate, cupric
hydroxide, basic copper carbonate, basic copper chloride and the
like for a method for treating bodies of water to arrest or
eliminate the growth of algae and aquatic weeds by giving a more
efficient algaestat, algaecide and/or herbicide, when the copper
salts or insoluble basic copper salts are used as a complex with an
alkylene diamine, such as ethylenediamine, propylenediamine and
substituted derivatives of these; or poly (aminoalkylene).sub.n
--NH.sub.2 wherein n is from 2 to 4, 5 or 6 such as diethylene
triamine, triethylene tetraamine, tetraethylene pentaamine,
dipropylene triamine, or mixtures of each of these with the others,
including diamines, such as aminoethyl ethanolamine and mixtures of
same with the other amines; in the complex a high copper content in
useful form is achieved and the effect of the complex on the weeds
is prolonged and noteworthy; as against previous copper compounds
which require the use of an organic herbicide such as 1,1'
ethylene-2,2' dipyridinium dibromide, (DIQUAT.sup.R) with the
copper compound to produce satisfactory herbicidal action at safe
and economic copper levels, the herein disclosed and claimed copper
and alkylene diamine complex is used alone for aquatic weed
control.
Inventors: |
Meyers; Marion D. (Houston,
TX), Stoner; Graham A. (Houston, TX) |
Assignee: |
Sandoz, Inc. (East Hanover,
NJ)
|
Family
ID: |
27033541 |
Appl.
No.: |
05/935,594 |
Filed: |
August 21, 1978 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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443493 |
Feb 19, 1974 |
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Current U.S.
Class: |
504/152 |
Current CPC
Class: |
A01N
59/20 (20130101); A01N 33/04 (20130101) |
Current International
Class: |
A01N
33/00 (20060101); A01N 33/04 (20060101); A01N
59/16 (20060101); A01N 59/20 (20060101); A01N
033/04 (); A01N 059/20 () |
Field of
Search: |
;71/66,67 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Vishnyakova et al., "Effect of Compounds Containing, etc.," (1972)
CA77, No. 1232d. (1972). .
Hall et al., "Polarographic Study of the Complexes, etc." (1972).
.
Laura et al. "Adsorption of EDA on Montmorillonite, etc.," (1970)
.
Wilson et al., "Botany" (1962). .
Holt, Rinehart & Winston, N.Y., Chicago etc., pp.
334,335,356,357 (1962)..
|
Primary Examiner: Hollrah; Glennon H.
Attorney, Agent or Firm: Sharkin; Gerald D. Vila; Richard
E.
Parent Case Text
This is a continuation of application Ser. No. 443,493 filed Feb.
19, 1974, now abandoned.
Claims
What is claimed is:
1. A method for combatting aquatic weeds growing in waters,
comprising dispersing in said waters an aqueous solution of a water
soluble complex of a divalent copper salt and an amine of the
formula:
wherein ALK is alkylene of 2 or 3 carbon atoms and each R is
independently hydrogen, methyl or ethyl, the amine to copper mol
ratio being from 1:1 to 10:1, in an amount sufficient to provide on
the basis of said waters a copper concentration of from 0.1 to 10.0
ppm, and thereby contacting said weeds with a herbicidally
effective amount of said complex.
2. The method of claim 1 in which the copper salt is selected from
the group consisting of copper hydroxide, acid copper sulfate, acid
copper chloride, acid copper acetate, acid copper nitrate, and acid
copper sulfamate.
3. The method of claim 2 in which the copper salt is acid copper
sulfate or copper hydroxide.
4. The method of claim 3 in which the amine is ethylenediamine,
N-methylethylenediamine or 1,2-propylenediamine.
5. The method of claim 4 in which the amine is ethylenediamine.
6. The method of claim 5 in which the mol ratio of amine to copper
is 2:1.
7. The method of claim 6 in which the copper salt is copper sulfate
pentahydrate.
8. The method of claim 7 in which Hydrilla Verticillata is
combatted.
9. The method of claim 7 in which Egeria Densa is combatted.
10. The method of claim 1 in which the amine is
ethylenediamine.
11. The method of claim 4 in which the amine is
N-methylethylenediamine, the copper salt is copper sulfate and the
mol ratio of such amine to the copper sulfate is 2:1.
12. The method of claim 4 in which the amine is
1,2-propylenediamine, the copper salt is copper sulfate and the
mole ratio of such amine to the copper sulfate is 2:1.
13. The method of claim 1 or 5 in which the weeds as selected from
the group consisting of Naiad, Vallisneria, Hydrilla, Milfoil,
Hyacinths and Egeria Densa.
14. The method of claim 1, 5, 7 or 8 in which the amount of the
complex is sufficient to provide on the bais of said waters a
copper concentration of from 0.3 to 6.0 ppm.
15. The method of claim 1, 5, 7 or 8 in which the amount of the
complex is sufficient to provide on the basis of said waters a
copper concentration of from 0.5 to 1.0 ppm.
Description
This invention relates to an algaecide and aquatic weed herbicide
composition and, more particularly, to an algaecide and aquatic
weed herbicide composition of copper salts and copper salts as a
complex either as the water soluble acid or insoluble basic
compounds with an alkylene diamine, triamine, tetraamine or
pentaamine.
BACKGROUND FOR THE INVENTION
Numerous bodies of water such as rivers, lakes, ponds, streams,
brooks, drinking water supplies, irrigation systems, agricultural
water systems, fish ponds, swimming pools, shower rooms and
industrial water systems, such as cooling towers and ponds, are
frequently polluted by an excessive growth of algae and other
microorganisms which impart an unacceptable quality to the body of
water. Moreover, some of the enumerated bodies of water develop
excessive aquatic weed growth which interferes with the flow of
water and renders the body of water unsuitable for the intended use
or diminishes the economic value of it. The particularly noxious
aquatic weed of economic importance is Hydrilla Verticillata, which
is commonly controlled by application of copper materials along
with an organic herbicide such as 1,1'-ethylene-2,2'-dipyridinium
dibromide. Weeds and algae in the recited bodies of water are
controlled by various means including chemical algaestats,
algaecides and herbicides. Not all of the chemicals used are fully
effective algaecides and few have useful herbicide properties and
then only against limited numbers of weeds.
THE PRIOR ART
For the control of the algae, the prior art has used, with
considerable success, acid or water soluble salts of copper as
inorganic or organic salts, e.g., copper sulfates, chlorides,
bromides, acetates, nitrates, citrates or the like. The inorganic
acid copper salts are disclosed in U.S. Pat. No. 2,734,028 and are
used in the form of a complex with an alkanolamine; the acid salts
of copper compounds reacted with aliphatic hydroxy acids are
disclosed in U.S. Pat. No. 2,400,863.
However, the stability of the copper salt and its complex has left
much to be desired and further improvements have been shown in U.S.
Pat. No. 3,716,351 which patent discloses an algaecide composition
containing a complex of a water soluble salt with an alkanolamine
and stabilizers therefor. For stabilizing the copper salts against
decomposition to elemental copper and/or cuprous oxide in storage
in the last mentioned patent, it has been taught that an effective
amount of an acetylenic diol and an alkali metal halogenate
prevents the copper alkanolamine complex from decomposing during
the periods of storage. In U.S. Pat. No. 3,716,351 it has been
mentioned specifically that the additives are for preventing the
complex from decomposing during extended periods of storage.
Further, in U.S. Pat. No. 2,734,028, it has been mentioned that in
alkaline waters with a pH over 7 (and, particularly, in waters
containing carbonates or bicarbonates), the copper sulfate is
generally ineffective due to the waste caused by precipitation of
copper in the form of either insoluble copper hydroxide or copper
carbonate.
Still further, while the composition described in U.S. Pat. No.
2,734,028 has been alleged to be useful as a herbicide, the amount
of the composition which has to be used to achieve the desired
results make it uneconomical or unduly toxic and hence unacceptable
except for a limited number of weeds (cf. Sutton et al., "Uptake of
Copper in Hydrilla", Weed Res., Vol. 11, Page 47 (1971)). Another
improvement in a prior art copper algaecide has been disclosed in a
companion application Ser. No. 397,136 filed Sept. 13, 1973. For
example, to control Hydrilla Verticillata, the amount of copper
compound used can be decreased to an economic level when the copper
compound is used in combination with another herbicide such as the
organic 1,1' ethylene-2,2' dipyridinium dibromide (cf. Sutton et
al., "Effect of DIQUAT on Upstake of Copper in Aquatic Plants",
Weed Sci., Vol. 18, Page 703 (1970)).
BRIEF DESCRIPTION OF THE INVENTION
It has now been found that contrary to the prior art teaching, the
use of basic copper salts such as cupric hydroxide, base copper
carbonate, basic copper chloride, basic copper sulfate and the like
and acid copper salts such as copper sulfate, copper chloride, etc.
results in unexpectedly beneficial composition for a method for
treating the enumerated bodies of water to arrest or eliminate the
growth of algae and aquatic weeds by giving a more efficient
algaecide and herbicide, when the water soluble acid copper salts
or insoluble basic copper salts are used as a complex with an
alkylene diamine, such as ethylenediamine, propylenediamine,
N-methyl ethylenediamine, N,N'-dimethyl-1,3, propanediamine,
N-methyl,1,3-propanediamine, N,N,N'N'-tetraethylethylenediamine, or
poly(aminoalkylene--NH.sub.2 wherein n is from 2 to 4 or 5 such as
diethylene triamine, triethylene tetraamine, tetraethylene
pentaamine, or mixtures of each of these with the others. Other
useful diamines are aminoethyl ethanolamine and mixtures of it with
the other amines. The improved herbicidal action of the disclosed
complex is especially noteworthy, more so, because solutions of
this complex can be used in practical economical and ecologically
safe amounts without additional herbicidal compounds as required
when using copper salts or complexes as in the prior art.
Still further, the same high copper content is achieved and the
effect of the complex on the weeds is prolonged and noteworthy.
(Table I).
TABLE I
__________________________________________________________________________
CONTROL OF HYDRILLA VERTICILLATA WITH DIFFERENT COPPER
MATERIALS.sup.a Percent Control at Different Copper Rates After
Exposure 2 Weeks 4 Weeks Copper Source.sup.b % Cu 0.1 ppm Cu 0.4
ppm Cu 0.1 ppm Cu 0.4 ppm Cu
__________________________________________________________________________
Copper Sulfate-EDA Solution 8 7 45 17 78 Copper Hydroxide-TEA.sup.e
Solution.sup.- 8 0 17 0 40 Copper Sulfate-TEA Solution 7.1 0 5 5 20
Copper Sulfate Pentahydrate Crystals 25.2 0 5 0 23 Copper Carbonate
(MALACHITE) 55 0 0 0 0 Copper Hydroxide-TEA Solution + DIQUAT 8
8.sup.C 78.sup.d 37.sup.c 89.sup.d
__________________________________________________________________________
.sup.a Experiments conducted in a controlled, environmental
laboratory. .sup.b Ethylenediamine = EDA .sup.c 0.25 ppm Cu and 0.1
ppm DIQUAT .sup.d 0.50 ppm Cu and 0.1 ppm DIQUAT .sup.e
Triethanolamine-
DISCUSSION OF THE INVENTION
As an alkylene amine useful in the present formulation of the
copper complex compositions, di-, tri-, tetra or penta amines
having from 2 to 4, 5 or 6 carbon atoms in the alkylene group are
employed as well as amino alkylalkanol amines having from 2 to 4 or
5 carbon atoms in the alkyl and alkanol group, e.g., amino ethyl
ethanol amine. These di- and tri-, tetra-, and pentaamines consist
of ethylene diamine (EDA), diethylene triamine, triethylene
tetraamine, tetraethylene pentaamine; propylene diamine,
dipropylene triamine and the like as well as mixtures of these and,
in addition, N-alkyl substituents of said amines. The preferred
compound is ethylene diamine and the preferred combination of it is
with copper sulfate pentahydrate or basic copper salt, such as
copper hydrate or copper hydroxide. A formulation for the copper
salt complex with the alkylene diamine or the other amines can
range from a ratio of 1:1 to 10:1 amine to copper based on the
number ratio of the copper salt and the amine molecules; it has
been found that a formulation of copper with ethylene diamine with
an amine to copper ratio of 2:1 is very acceptable.
A complex of copper (II) with two moles of ethylene diamine is
chemically stable (stability constant, log K=20.03) and thus is a
useful complex in the control of algae and weeds.
Of the basic copper salts, various forms of copper hydroxide
(Cu(OH).sub.2) (cupric) have been found to be the most
advantageous. Copper hydroxide is synonymous with cupric hydroxide,
copper hydrate, hydrated copper oxide, etc. The copper alkylene
di-amine complex is prepared by dissolving copper hydroxide or
hydrated copper oxide in an aqueous solution of one of the above
recited alkylene amines.
A water soluble di, tri, tetra or pentaamine is required or the
reaction product (complex) must be water soluble.
A representative reaction of the copper compound and amine is
depicted as follows
In the examples to follow various embodiments of the invention are
illustrated.
EXAMPLE 1
One mole of copper sulfate pentahydrate (CSP) crystals was reacted
with two moles of reagent grade 91-93% ethylenediamine (EDA diluted
with water). The reaction was very exothermic and copper sulfate
pentahydrate was added stepwise during 30 minutes to keep the
temperatures below 70.degree. C. The dark purple solution was
diluted with water to 7% copper. The properties of the solution
were: pH 11.5; 1.182 specific gravity at 25.degree. C.; and 13.6
cps viscosity at 25.degree. C.
EXAMPLE 2
To the Cowles dissolver were added 150 gallons of water and one
drum 414 pounds, of 99% ethylenediamine. The temperature of the
stirred solution was 56.degree. C. Stirring was continued as 400
pounds of copper sulfate pentahydrate (CSP), crystals (100% through
30 mesh and 95% retained on 100 mesh screen) were added over a
period of five minutes; the temperature rose to 68.degree. C. One
hundred pound quantities of CSP crystals were added at one-half
hour intervals until a total of 860 pounds were used. The
calculated EDA:Cu molar ratio was 1.998:1 based on copper analysis
of 25.19% for the CSP crystals. Solution pH was 8.0 after the
addition of 26 gallons of water and 11 pounds 99% EDA and further
stirring for 15 minutes, the copper content was 8.12% with specific
gravity 1.224 at 25.degree. C., pH 10.6. A total of 240 gallons of
product was packaged in five gallon containers. Summary of the
analytical and physical data for the solution of the complex is in
the following Table II.
TABLE II ______________________________________ PROPERTIES OF
(BIS-ETHYLENEDIAMINE) COPPER SULFATE FOR EXAMPLE 2 Analyses Actual
Calculated.sub.a ______________________________________ Cu 8.12%
8.00% C 6.48% 6.05% H 9.32% 9.28% N 7.31% 7.05% SO.sub.4
11.13.sub.b % 12.08% pH 10.6% -- Density, 25.degree. C. 1.224 gm/cc
-- Viscosity, 25.degree. C. 14.5% cps -- Color Deep Purple --
______________________________________ .sub.a Based on aqueous
solution containing 8% metallic copper and molar ratio of 2:1 amine
to copper. .sub.b Based on total sulfur content of 3.71
percent.
Crystals of bis(ethylenediamine) copper (II) sulfate were
precipitated in 100% yield from an 8% solution by the addition of
five volumes of 95% ethanol. The crystals were isolated by
filtration; the resulting filtrate was colorless and free of
copper. The product was dried overnight in a vacuum oven at
30.degree. C. Analysis for copper, sulfur, carbon, hydrogen and
nitrogen all conformed to the formula Cu(EDA).sub.2 SO.sub.4.
TABLE III ______________________________________ ANALYSES OF SOLID
BIS (ETHYLENEDIAMINE) COPPER (II) SULFATE % Calculated for
Cu(NH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2).sub.2 Found %4
______________________________________ Cu 22.78 22.6 SO.sub.4 34.33
34.5.sup.a C 17.3 16.95 H 5.77 5.89 N 20.2 19.96 Loss, 100.degree.
C. 0 0.1 ______________________________________ .sup.a Calculated
from 11.5% S found.
Significant control of hydrilla was obtained with this material
when used in treated ponds at copper concentrations as low as 0.5
ppm. based on copper in the water.
EXAMPLE 3
To a solution of 133 g. anhydrous EDA (98%) in 273 ml water was
added slowly 117 g. copper hydroxide. The copper hydroxide
dissolved rapidly. The addition was regulated to keep the
temperature below 50.degree. C. After complete dissolution of the
solid, 273 ml water was added. The resulting solution was
purple-blue as compared to the deep purple solution from the copper
sulfate product. After stirring and cooling to 25.degree. C., the
following properties were found for the solution: 8.1% Cu, pH
greater than 14, density 1.138, and viscosity 12 cps. After
standing one week, a yellow-orange deposit was observed in the
bottom of the container. The supernatant liquid was decanted and a
new yellow deposit formed after another week storage.
EXAMPLE 4
In a similar procedure, as described in Example 3, 102 g. of copper
hydrate (1 mole Cu) was added to 145 ml 91-93% ethylenediamine
(EDA-2 moles) in 561 ml water. The hydrate dissolved rapidly when
initially added to the EDA solution at 50.degree. C. However, the
temperature dropped and stirring for 4 hours at 30.degree. C. was
required to achieve complete dissolution. The final solution was a
deep blue color. Properties of the liquid were: 8.15% Cu; pH
greater than 14; density, 1.136 at 25.degree. C.; and viscosity,
14.5.
As mentioned above bis(ethylenediamine) copper (II) have been
prepared by the reaction of ethylenediamine with copper hydrate and
copper hydroxide. However, the pH of these solutions is
considerably higher (greater than 14) than the solutions made from
copper sulfate (pH 9.0-11). These solutions are as a result less
stable upon standing than those made with copper sulfate, but can
be stabilized by adjusting the pH to between 9 to 11 by the
addition of a mineral acid.
EXAMPLE 5
In a similar procedure, as described in Example 1, 131 grams of CSP
were reacted slowly with 82 grams, 90% 1,2-propanediamine in
aqueous solution. The reaction mixture rose to 69.degree. C. After
one hour the solution was diluted with water to give an 8.01%
copper content. Other properties of the solution were: pH, 10.7;
density at 25.degree. C. 1.22 grams per cc; and viscosity, 20
cps.
Other copper complexes with aminoethylethanolamine,
diethylenetriamine, triethylenetetramine, 1,3-propylenediamine,
N,N'-dimethyl-1,3-propylenediamine, N-methyl-1-3 propylenediamine,
and tetraethylene-pentamine, have also been prepared from copper
sulfate and/or copper hydrate.
Generally, a ratio of about 2 to 1 of the amine to copper is used
in a solution of 8% copper; the solubility is reduced with
increasing amounts of higher alkylene di and triamines (water
solubility decreases with each additional carbon atom in the
alkylene herein, unless ionic groups are introduced). Copper
content may range from 1-12%. An 8% copper solution is the
preferred formulation; Table IV gives the chemical and physical
properties for this preferred formulation.
TABLE IV ______________________________________ Bis
(Ethylenediamine) Copper (II) Sulfate Complex solution and its
properties for the use of it as an aquatic herbicide. Chemical
Composition Normal Cu:EDA ratio 1:2 Cu metallic, % 8:0 EDA, % 15.24
H.sub.2 O, % 64.67 Physical Properties Density, g/cc 25.degree.
1.22 pH 10.0 Viscosity cps 14.5 Color Deep Purple
______________________________________
EXAMPLE 6
As in Example 5, 131 grams CSP were added to an aqueous solution
containing 96.2 grams N-methylethylenediamine. After stirring for 8
hours and diluting the solution to a copper content of 8.09%, the
properties of the solution were as follows pH, 11.9; density at
25.degree. C., 1.215 grams per cc; and viscosity at 25.degree. C.,
24 CPS.
Solutions containing 8% copper were prepared with ethylenediamine
ratios of 2:1 mol EDA to copper using cupric chloride
(CuCl.sub.2.2H.sub.2 O), copper acetate (Cu(CH.sub.3
CO.sub.2).sub.2. H.sub.2 O), copper nitrate
(Cu(NO.sub.3).sub.2.3H.sub.2 O) and copper sulfamate (Cu(SO.sub.3
NH.sub.2).sub.2) solutions.
UTILITY OF THE INVENTION
The copper ethylene diamine complex may be employed by introducing
the solution in any of the desired bodies of water in amounts up to
from 0.1 ppm to 10 ppm expressed as copper. Generally from 0.5 ppm
to 1.0 ppm is employed, although a range from 0.3 to 6 ppm is
practical, broad range.
It has also been found that the fish toxicity (an undesirable
phenomenon) of the herein disclosed algaecidal and herbicidal
composition favorably compares with any of the existing algaecides
and herbicides based on copper complexes. For example, the
mortality, expressed as LC 50 (lethal concentration) in parts per
million of copper of bluegill sunfish was 46.0 ppm at 24 hours and
30 ppm at 96 hours for the copper sulfate ethylene diamine complex.
The improvement over the prior art complexes such as shown in U.S.
Pat. No. 2,734,028 is about tenfold; same order of improvement is
observed over copper sulfate.
A noticeable improvement was observed vis-a-vis the prior art
compounds in respect to rainbow trout.
In respect to mammalian toxicity, the EDA-CSP complex has a low
mammalian toxicity and comparable to the copper triethanolamine
complex.
The algaecidal-herbicidal composition, as mentioned above, may be
sold in the form of crystals, or slowly dissolving pellets or in a
properly diluted water solution, or in conjunction with suitable
extenders and diluents such as talc, clay, starch, gelatin and
formulated with suitable surface active agents.
Because of greater stability, and use at higher pH values, the
presently disclosed compositions are useful in irrigation systems
in the Western United States because alkaline water is encountered
in these systems.
The range of pH conditions within which the disclosed complexes are
useful in between 7 to 11; a broader and still operative range is 6
to 12.
The algaecidal composition is effective against all common forms of
algae, including filamentous algae, such as Cladophora and
Spirogyra, planktonic algae such as Microcystis and Anabaena,
branched algae such as Chara vulgaris and Nitella, swimming pool
algae, commonly referred to as black, brown and red algae, and
algae found in ponds such as Dictyosphaerium, Spirogyra,
Oedogonium, Chlorococcum, Pithophora, Hydrodictyon, and
Lyngbya.
TABLE V ______________________________________ ACTIVITY OF A
SOLUTION OF EDA-CSP CRYSTALS FOR CERTAIN ALGAE SPECIES Minimum
Copper Concentration (ppm) Algistatic Algicidal (Prevent (Kill
Algae Growth) Growth) ______________________________________
Microcystis aeruginosa 0.01-0.02 0.01-0.02 Lyngbya versicolor 0.25
1.0 Pithophora oedogonium 0.04-0.08 0.08-0.17 Phormidium inundatum
Allen's Medium (pH 7.0) 0.83 None Gorham's Medium (pH 8.5) 1.00
None Chlorella pyrenoidosa Allen's Medium (pH 7.0) None None
Gorham's Medium (pH 8.5) None None
______________________________________
Although in respect to some copper resistant algae the complexes
described in the previously mentioned companion application is more
effective, the overall herbicidal and algaecidal and algaestatic
properties of the present compounds are outstanding, especially the
herbicidal properties.
In respect to the herbicidal properties the following weeds, as an
illustration, are subject to an effective attack by the disclosed
compounds: Naiad, Vallisneria, Hydrilla, Milfoil, Hyacinths and
Egeria Densa. Data for control of the noxious weed Hydrilla
verticillata by typical examples of different copper diamine
complexes are given in Table VI.
TABLE VI ______________________________________ EVALUATION OF
COPPER DIAMINE COMPLEXES % Control of Hydrilla Weeks After Cu Rate
Treatment Solution ppm 2 4 ______________________________________
CuSO.sub.4 .2(ethylenediamine) 0.5 96 93 complex CuSO.sub.4
.2(N--methyl ethylene- diamine) complex 0.5 93 93 CuSO.sub.4 .2(1,2
propanediamine) complex 0.5 98 97 CuSO.sub.4 .2(1,3 propanediamine)
complex 0.5 15 37 CuSO.sub.4 .(tetraethylenepentamine) complex 0.5
20 23 Cu(OH).sub.2 .2(aminoethylethanol- amine) complex 0.5 70 75
ethylenediamine (EDA) Tested at 5.0 ppm EDA 0 0 0 Mixture
CuSO.sub.4 .2(ethylenediamine) 50% 0.5 68 77
Cu(OH.sub.2).2(triethanol- 50% amine) Cu(OH).sub.2
.2(ethylenediamine) complex 0.5 92 88
______________________________________
TABLE VII ______________________________________ EVALUATION OF
FIELD TEST PLOTS ALGAE AND WEEDS Plot.sup.b Aqueous Organic 5 Week
No. Tank Tank Evaluation ______________________________________ 1
16 gal. EDA-CSP.sup.a + 3.0 gal. SPRA- 85% control 70% 60 gal.
water MATE open water most 15.0 gal. impressive of all xylene
plots. Clean bot- tom, with small fragile sprigs of regrowth in 1/3
of area. 2 8 gal. EDA-CSP.sup.a + 3.0 gal. SPRA- 80-85% Control- 4
gal. AQUA-K.sup.d + MATE + Excellent control- 60 gal. water 15.0
gal. bottom clean, sur- xylene face covered with mass of yellow
defoliated stems, completely mushy. 3 8 gal. EDA-CSP.sup.a + 15.0
gal. 85-90% Control 4 gal. DIQUAT.sup.c + xylene Plot still loose
63 gal. water 3.0 gal. SPRA- and coming off MATE bottom, with com-
pound remaining in area. Plot area is still free of hyacinths after
5 weeks. ______________________________________ .sup.a Amounts of
copper present 0.5, 0.25, and 0.25 ppm for plots 1 to 3
respectively. .sup.b All treatment areas were two surface acres
approximately five feet in depth. .sup.c 1,1' ethylene2,2'
dipyridinium .sup.d Further combinations of the algaecide with
AQUAK.RTM. as an adjuvant. (AQUAK is `The dipotassium salt of 3,6
endoxohexahydrophthalate`-
TABLE VIII
__________________________________________________________________________
EVALUATIONS OF FIELD TEST PLOTS - HERBICIDAL ACTIVITY Other Surface
Organic Adju- In- Organic No. Areas Copper Herbicidals vants vert
Phase Evaluation
__________________________________________________________________________
1 1 acre EDA-CSP None None No -- Excellent 18 gal..sup.a control
(slight regrowth) 2 1 acre TEA-Cu ALIQUAT.RTM. None No -- Good con-
4 gal. 21.sup.b f trol (re- 3.2 gal. growth) 3 1 acre EDA-CSP NONE
None No -- Good con- 20 gal..sup.a trol 4 1 acre EDA-CSP.sup.b
DIQUAT.sup.g AMMATE.RTM. .sup.d 0.5 gal. Die- Excellent 4 gal. 2
gal. 25 lbs. S-120.sup.h sel control 5 1 acre Cutrine.RTM. DIQUAT
AMMATE 0.5 Die- Excellent .sup.b e 2 gal. 25 lbs. gal. sel control
4 gal. S-120 6 Strip EDA-CSP.sup.b DIQUAT AMMATE 0-5 Die- Excellent
9' .times. 400' 4 gal. 2 gal. 25 lbs. gal. sel control S-120
__________________________________________________________________________
.sup.a Equivalent to 1 ppm copper on acre foot basis. .sup.b
Equivalent to 0.25 ppm copper on an acre foot basis. .sup.c All
invert treatments were applied through hoses dragged on the bottom;
the inverts were formed as a tank mix prior to application. .sup.d
AMMATE also has herbicidal activity. Control due to AMMATE alone i
unknown; AMMATE is ammonium sultemate. .sup.e Reportedly the
composition disclosed in U.S. Pat. No. 2,734,028. .sup.f Aliquat 21
is trimethyl coco ammonium chloride. .sup.g Identified above .sup.h
S-120 is an emulsifier available from the source identified
below.
TABLE IX ______________________________________ RATINGS OF
COMMERCIAL AND EXPERIMENTAL HERBICIDES FOR CONTROL OF EGERIA DENSA
Treatments Control Rating* ______________________________________
Bis(ethylenediamine) copper (II) 8.5 (EDA-CSP), 8 gpa Diquat 2 gpa
+ K-lox.RTM., 4 gpa 6.5 Diquat 2 gpa + EDA-CSP, 4 gpa 5.5 Diquat 2
gpa 4.5 K-lox, 8 gpa 2.5 Check 1.5
______________________________________ K-lox is a complex of cupric
hydroxide and triethanolamine of 8% copper solution, by weight.
*Means represent an average of visual ratings of two 1/2 acre plots
where a rating of zero represents no egeria control and a rating of
10 represents complete control. gpa = gallons per surface area
acre; 16 days after treatment. Treatments were applied in a volume
of 200 gpa through trailing hoses at an approximate depth of 6 ft.;
copper is at 8% by weight of solution.
Field evaluations of the bis(ethylenediamine) copper complex have
been very good. Excellent control of Hydrilla has been achieved
with this complex when applied at 0.5 and 1.0 ppm copper or in
combination with DIQUAT.sup.R or ENDOTHALL.sup.R disodium
3,6-endoxohexahydrophthalate. A solution of the EDA-CSP complex
such as described in Example 2 can be inverted easily with
emulsifiers such as SPRA-MATE (acid salt of a fatty amine from KDM
Company, San Antonio, Texas) or S-120 (an emulsifier available from
Standard Spray and Chemical Company, Lakeland, Fla.).
Results of field test evaluations of the bis(ethylenediamine)
copper (II) complex used alone as a diluted liquid and with
adjuvants are given in Tables VII, VIII, and IX. Table VII is a
comparison of the copper ethylenediamine complex with and without
the addition of an organic herbicide, DIQUAT.sup.R
(1,1'-ethylene-2,2'-dipyridinium dibromide). Table VIII is the
evaluation of field plots for the copper diamine complex as well as
other copper-organic complexes with organic herbicides as
adjuvants. Table IX compares the results obtained with the above
named complex and other recommended standard herbicidal treatments
for Egeria densa. The rate of the effective action of the EDA-CSP
is noteworthy.
Corrosion studies show that a solution of EDA-CSP complex is
slightly more corrosive than basic copper hydratetriethanol amine
to aluminum and mild steel, but much less corrosive than a complex
disclosed in U.S. Pat. No. 2,734,028 or copper sulfate.
In addition to the above desirable salts, the following copper
salts are useful for forming the described complex: copper bromide,
chlorate, citrate, formate, oxalate, benzoate, tartrate and the
like.
* * * * *